Process for the preparation of polymeric aminoalkyl-vinyl ethers



2,871,203 Patented Jan. 27, 1959 PROCESS FOR THE PREPARATION OF POLY-MERIC AMINOALKYL-VINYL ETHERS No Drawing. Application September 30, 1955Serial No. 537,901

4 Claims. (Cl. 260-21) This invention relates to a process for producingpolymers of aminoalkyl vinyl ethers and derivatives thereof, and it isespecially concerned with the production of homopolymers and copolymersof aminoalkyl vinyl ethers of high molecular weight in an efiicientmanner. It also includes novel polymers. This application is acontinuation-in-part of my copending application Serial No. 474,002,filed December 8, 1954.

Aminoalkyl vinyl ethers cannot be polymerized alone, or with a minorproportion of another type of monoethylenically or polyethylenicallyunsaturated monomer, by means of such initiators as benzoyl peroxide andrelated peroxygen compounds. While azo catalysts can be used topolymerize aminoalkyl vinyl ethers, a large projportion, on the order ofto based on the weight of the monomer, of the initiator is required andthe highest molecular weight homopolymers obtainable have an average ofabout 1000 to 2000 molecular weight. Copolymers may be made of somewhathigher weight depending upon the proportion of monomeror monomers ofother than vinyl ether type used. When attempt is made to copolymerizethe aminoalkyl vinyl ether with a cross-linking monomer, such asdivinylbenzene, there is insufiicient copolymerization of the amine withthe crosslinking agent to convert the copolymer to insoluble form, thatis, to a form insoluble in both aqueous and organic solvent systems. 7

Also, certain substituted aminoalkyl vinyl ethers, such as those inwhich the N atom carries a polymerizationinhibiting group, such as abenzyl, substituted benzyl, or a nitrophenyl group, polymerize in thepresence of an azo catalyst only to a small extent of 5% to to lowaverage molecular weights of about 1000.

It is a primary object of the present invention to produce polymers ofaminoalkyl vinyl ethers by a process adapted to provide such polymers,of any molecular weight desired including higher molecular weights of5000 to 50,000 or more, whether the polymer is a homopolymer or acopolymer. An ancillary object is to pro.- vide a process capable ofproducing high molecular weight copolymers of cross-linked insolubletype from aminoalkyl vinyl ethers. Another object is to producesubstituted aminoalkyl vinyl ether polymers of high or low molecularweight which have not heretofore been known and which cannot be obtainedby simple or direct polymerization of corresponding monomers because ofthe instability of the monomers which either cyclize to destroy thevinyl unsaturation or hydrolyze at the ether linkage. Other objects andadvantages will be apparent from the description thereof hereinafter.

In accordance with the present invention, an amidoalkyl vinyl ether ispolymerized to the molecular weight desired and the resulting polymer ishydrolyzed to provide a poly(aminoalkyl vinyl ether). The 'amidoalkylvinyl ether may be a carbonamidoalkyl vinyl ether or a care bamidoalkylvinyl ether, the latter type of compound being known also as aureidoalkyl vinyl ether. The amidoalkyl vinyl ethers that may be used incarrying'out the United States Patent Ofifice process of the presentinvention are those having the structure of one of formulas I and H:

CH CHOANRCONH II CH '=CHOANRCOR wherein A is an alkylene group of 2 to 3carbon atoms of which at least two separate the adjoining O and N atomsI R is H or CH;

and R' is H or an alkyl radical of 1 to 4 carbon atoms. Specificcompounds within the scope of Formula I and II which may be used'includethe following:

CHFCHOCH2CH2NHCONH2 CHFCHOCH2CH2N(CH3)CONH2 CH2Y=CHOCHQCHZCH2NHCONH2CH2=CHOCH2CH2CH2N(CH3)CONH2 CI-IFCHOCH(CH3)CH2NHCONH2CH2=CHOCH(CH3)CH2N(CH3)CONHZ CH2=CHOCH2CH(CH3)NHCONH2CHFCHOCH2CH(CH3)N(CH3)CONH2 CH2==CHOCH2CH2NHCOH CHFCHOCH2CH2NHCOCH3CHFCHOCHZCHZNHCOQHE vThe amidoalkyl vinyl ethers are readily polymerizedto produce homopolymers as well as copolymers having a wide range ofmolecularweights including molecular weights of 5000 to 50,000 or more.They may be polymerized in the presence of catalysts or initiators ofthe acyclic .azo type. group is attached to aliphatic carbon atoms, atleast one of which is tertiary. Typical azo catalysts areazodiisobutyronitrile, azodiisobutyramide, dimethyl (or diethyl ordibutyl) azodiisobutyrate, azobis(a,'y-dimethylvaleronitrile) azobisa-methylbutyronitrile) azobis a-methylval'eronitrile), dimethyl,azobismethylvalerate, and the like. In these catalysts one of thecarbons bonded to the tertiary carbon atom has its remaining valencessatisfied by at least one elementfrom the class consisting of oxygen'andnitrogen. Polymerization may be effected in bulk, in solution, or inemulsion systems. To effect polymerization the amidoalkyl vinyl etherand the acyclic azo catalyst are mixed directly or in the presence of aninert solvent and the mixture is maintained between 60 and 100 C. untilthe desired extent of polymerization is attained. For water-solubleamidoalkyl vinyl ethers water may serve as solvent, if desired. Othersolvents include methanol, ethanol, isopropanol, butanol,dimethylformamide, benzene, toluene, ethyl acetate, etc. The amount ofcatalyst may be varied from about 0.1% to about 5% of the weight of theamidoalkyl vinyl ether. The polymerization is best carried out in aninert atmosphere such as nitrogen gas.

For polymerization in solution, concentrations of monomer from about 50%to about are generally desirable. The course of polymerization may bereadily followed from the increase in viscosity of the solution. Thecatalyst may be added in increments, if desired, with or withoutadditional solvent.

In such compound the -N=N 5i "'A'50'%"'aqi1e6us"saiuaen' of a water'solubl'e ureidoalkyl vinyl ether has a viscosity of less than A on theGardner Holdt scale. After. polymerization at 7 5 C.

for 16 hours the viscosity is manl B ltoiD, but may be carried to 2., asconversion is carried runner.

Polymerization in dimethylform'a'm'ide results in a conversion ofmonomer to polymerat least as high as in water and usually higher for agiven amount of catalyst, but the polymer formed is of lower molecularsize than polymers formed 'in water. For example, a 50% solution ofureidoethyl vinyl ether in dimethylformamidc held at 75 C. for 16 hoursreadily develops a viscosity of G to; I. on the Gardner-Holdt scale,;but conversion may be carried to a viscosity from D to Z The polymerhere isheld insolution by the presence of monomer in thedimethylformamide, for after monomer and polymer are separated, thepolymer does not redissolve in pure dimethylformamide For bulkpolymerization the preferred temperatures are from about 70 to about 80C. "and the optimum proportion of-catalyst is from 0.3% to 1% of theweight of the amidoalkyl vinyl ether. Under a nitrogen atmosphere asatisfactory degree of polymerization is obtained in to hours.

The homopolymers that result are generally soluble substances, Theamidoalkyl vinyl ethers may also be copolymerized with monoethylenicallyunsaturated polymerizable compounds, such as vinyl chloride, vinylbromide, vinyl iodide, 1,1-difiuoroethylene, 1,1-dichloroethylene;vinylidene hydrocarbons such as isobutylene, l,3-butadiene,;styrene;halovinylidene hydrocarbons such as 2-fluoro-l,3-butadiene,2-chloro-l,3.-butadiene, 2,3-di-.

chloro-l,3-butadiene; acrylic, halocrylic and alkacrylic esters,nitriles and amides such as ethyl acrylate, methyl methacrylate, butylmet hacrylate, methoxymethyl methacrylate, chloroethyl inethacrylate,beta-diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile,acrylamide, methacrylamide; vinyl carboxylates such as vinyl formate,vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl laurate;unsaturated aldehydes and ketones such as acrolein, methacrolein, methylvinyl ketone; N-vinyl imides such asN-vinylphthalimide,N-vinylsuccinimide; unsaturated ethers such as vinylethyl ether, other vinyl monomers such as vinylpyridine,N-vinylcaprolactam; and other polymerizable or copolymerizableunsaturates such as tetrafluoroethylene, diethyl fumarate, dimethylmaleate and the like.

When a water-insoluble comonomer is copolymerized with the amidoalkylvinyl ether, the copolymerization may be effected by means of anemulsion system using suitable emulsifying or dispersing agents such asthe higher alkylaryl polyethoxyethanols such as the ethylene oxidemodified alkylphenols in which the alkyl group has from 8 to 18 or morecarbon atoms such as octyl, dodecyl, and octadecyl, and which containfrom 6 to 20 or more ethylene oxide. units per molecule.

The amidoalkyl vinyl ether may also be copolymerized withpolyethylenically unsaturated compounds including divinylbenzene, glycoldimethacrylate, trivinylbenzene, and N,N-bis-vinoxyethylurea.Thereafter, the amido groups are hydrolyzed to leave amino groups in thepolymer. Insoluble copolymers are thus obtainable. even with a smallproportion of the cross-linking monomer. Because of the high molecularWeight obtained, insuch copolymer a lower proportion of cross-linker isrequired in the final resin to produce and maintain insolubility afterhydrolysis to produce free amine groups. Because of this, there is agreater ion-exchange capacity obtainablein the ultimate copolymer.

The hydrolysis of the polymer of the amidoalkyl vinyl ether may beeffected under acid or alkaline conditions.

. An acid, such ashydrochloric, oxalic, or sulfuric'may be used.Preferably an alkaline material such as the "hydroxide or carbonate ofammonia, titanium, oran alkali z the acyl groups maybe completelyremoved by hydrolysis or only part of them may be removed if it isdesired to produce a copolymer containing both amine and amido groups.'Analogously, the hydrolysis of a binary copolymer of an amidoalkylvinyl ether with a comonomer of another type may be carried out in sucha manner as to remove only part of the acyl groups, thereby producing aternary copolymer, or complete hydrolysis of the acyl groups may beeffected, thereby producing a difierent binary copolymer. In any event,the hydrolyzed polymer or 'copolymer contains monomeric units having thestructure of Formulalll:

'oH2oH ANHR III

in which the symbols are as defined above.

The process of the present invention provides a practical and efficientway to produce high molecular weight aminolkyl vinyl ethers. Thehomopolymers of such compounds are valuable as additives to paper,especially in the heater, for imparting improved wet strength to theultimate paper produced. The higher the molecular weight of the polymerthat is used for this purpose, the greater the wet strength obtained fora "given amount of polymer added, or the lower the amount of additiveneeded to produce a given wet strength. This is'gener'ally' true whetheror not the addition is' made with or without formaldehyde or with orwithoutsubs'equ'ent treatment of thewet paper sheet just priort'o'dr'y'ing with formaldehyde. The polymers are usefulas 'bactericidesand fungicides, as Well as for modifying the dyeing properties of films,sheets and other'articles' produced from compositions to which theaminoalkyl vinyl ether polymers are added. The 'pol'ymers'may'be'incorporated in films orsheets of hydrophilic type," such as regeneratedcellulose, polyvinyl alcohol of cellulose acetate'to providepermselective membranes. In all such applications wherein the polymermay be-present within the body of a coating, a cast or extrudedarticle',or the like, the poly mers of higher molecular weight arele'ss"subjectto loss or migration from the coating or 'formedarti'cle during use,especially under conditions wherein contact with aqueous solutions isencountered.

Various derivative polymers can be obtained from the hydrolyzedarnidoalk'yl' vinyl ether'polymers by reaction with'the amino groupsobtained as a result ofthehydrd lysis. By' this procedure N-substitutedaminoalkyl vinyl ether polymers are obtained which could not be produceddirectly from corresponding N-substituted monomers because of theinstability ot such monomers or could not be produced in high molecularweights or with practical conversions from such correspondingN-substituted monomers of stable character. These" derivative polymerswhich are hereinafter described include (1) ce'rtain'polymericN-vinyloxyalkyl carbarnates and certain polymeric ureidoalkyl vinylethers which dono't exist in monomeric form because of'cycliz'ationwith' consequent destruction of vinyl unsaturation; '(2)certai'n'polymeric sulfonamido alkyl vinyl ethers whichin monomericform'hydrolyze at'the ether linkage becauseof'inh'erent acidity whenattempts are'made' to efiecfpolymerization; and(3)'polymericflaminoalkyl vinyl etliersh'aving'the N'atom sub stitutedwith inhibiting groups" such as b'nzylj substituted benzyl,and'nitrophenyl,

.ester may be used for this purpose.

Carbamate derivatives comprising polymerized N- vinyloxyalkyl carbamateunits Formula IV having the structure of mula III by-the reaction of thepolymer with an alkyl chlorocarbonate in which the alkyl group has from1 to 18 carbon atoms, such as methyl, ethyl, isopropyl, dodecyl oroctadecyl, in the presence of an acceptor of basic character for theacid generated, such as potassium carbonate, at temperatures of to +20C. in water or other aqueous media such as an aqueous alcohol solution.The reaction may be carried out for a period of l to 4 hours. Oneadvantageous procedure is to hydrolyze the amidoalkyl vinyl ether in thepresence of alkali at elevated temperatures, cool to below 20 C. andwith excess alkali still present, add the alkyl chlorocarbonate andreact for several hours at the low temperature. The products obtainedare inherently film-forming in character and are quite useful asplasticizers for cellulose derivatives, such as cellulose acetate orcellulose acetate butyrate. The higher molecular weight polymericcarbamates thus obtained may be incorporated in spinning solutions ofthe cellulose derivatives, such as in acetone, acetonitrile, ordimethylformamide which may then be spun into suitable coagulatingmedia, such as heated air or a Water bath to form films, sheets, fibersor the like. A proportion of 5% .to of the carbamate polymer based onthe Weight of the cellulose Analogous compounds made in the same wayfrom the poly(aminoalkyl vinyl ether) but with an aryl chlorocarbonate,such as phenyl chlorocarbonate or p-chlorophenyl chlorocarbonate arevaluable as plasticizers for vinyl resins, such as polyvinyl chloride,copolymers thereof with vinyl acetate, vinylidene chloride,acrylonitrile and the like. For these purposes, the high molecularweight of the polymeric carbamates serves to hinder diffusion of thepoly-- mer from plasticized masses containing them and from spinning orcasting solutions containing them, whether of cellulose ester type orvinyl resin type. Those polymeric carbamates comprising units having thestructure of Formula IV which have a hydrogen atom in the place of Rcannot be obtained from the corresponding monomer because of cyclizationas pointed out above.

Ureido derivative polymers comprising monomeric units having thestructure of Formula V in which A is as defined above and R and R may bethe same or difierent hydrocarbon substituents selected from the groupconsisting of cyclohexyl and alkyl groups having 1 to 18 carbon atoms,may be obtained from those polymers of aminoalkylvinyl ethers havingmonomeric units of Formula III by the reaction of the polymer with adisubstituted carbamyl chloride such as dimethyl carbamyl chloride,diethyl carbamyl chloride, dipropyl carbamyl chloride, di-isopropylcarbamyl chloride, dibutyl carbamyl chloride, di-isobutyl carbamylchloride, diamyl carbamyl chloride, dihexyl carbamyl chloride,dicyclohexyl carbamyl chloride, dioctyl carbamyl chloride, didecylcarbamyl chloride, didodecyl carbamyl chloride, dihexadecyl carbamylchloride, dioctadecyl carbamyl chloride, ditetraco-syl carbamylchloride, methyl ethyl carba-myl chloride, methyl propyl carbamylchloride, methyl isopropyl carbamyl chloride, methyl butyl carbamylchloride, methyl cyclohexyl carbamyl chloride, methyl octadecyl carbamylchloride, ethyl isopropyl carbamyl chloride, ethyl octylcarbamylchloride, ethyl hexadecyl 6 carbamyl chloride, butyl octadecyl carbamylchloride, hexyl octyl carbamyl chloride. The reaction may be effectedunder anhydrous conditions in an inert solvent,

such as toluene, with a basic acceptor for the acid generated, such asexcess of the polyamine or an inorganic base, such as sodium orpotassium carbonates at a temperature of 20 to C. When an inorganic baseis,

used, water is preferably added to the inert solvent. As in the case ofcarbamate polymers, the ureido polymers having units of Formula I inwhich R is H cannot be produced from corresponding monomers because oftheir cyclization.

The polymers of aminoalkyl vinyl ethers, and especially the highmolecular weight polymers obtainable in accordance with the presentinvention by the hydrolysis of amidoalkyl vinyl ethers, are also usefulfor the production of sulfonamide derivatives. amides) comprisepolymerized units having the structure of Formula VI ANRSOQR in which Aand R are defined above and R may be cyclohexyl, an alkyl group of 1 to6 carbon atoms, such as methyl, ethyl, phenyl, alkylphenyl, such astolyl, xylyl, chlorophenyl, dichlorophenyl, nitrophenyl, hydroxyphenyl,and the like. For making these poly(sulfonamides) the same procedures asoutlined above in relation to the production of the carbamates aregenerally employed except that the chlorocarbonates are replaced withsulfonyl chlorides, such as methyl sulfonyl chloride, benzene su1corresponding to the polymerized units of Formula VI- which have H asthe substituent R hydrolyze at the ether linkage because of inherentacidity when attempts are made to polymerize them; alsoN-methylnitrobenzenesulfonamidoalkyl vinyl ethers cannot be directlypolymerized to high molecular weight polymers because of the inhibitingefiect of the nitro group in monomers of this type. The polymericsulfonamides obtained are useful as plasticizers for cellulose esters,such as cellulose acetate and the polyvinyl resins, such as copolymersof vinyl chloride or vinylidene chloride with vinyl acetateoracrylonitrile, having the same advantages of freedom from migrationetc. mentioned in'connection with the poly(N-vinyloxyalkyl carbamates)above.

Under the same general conditions as used for making thepoly(sulfonamides), the aminoalkyl vinyl ethers react with isocyanates,such as p-chlorobenzyl isocyanate, or p-nitrophenyl isocyanate toproduce substituted ureas. As in the case of the p-nitrobenzenesulfonamide derivative just mentioned, high molecular Weight polymers ofthese types can be obtained by the process of the present invention,whereas they could not be obtained by the direct polymerization of acorrespodning monomer because of the inhibiting efiect of the benzyl andnitro groups.

Ion-exchange resins may be obtained from the aminoalkyl vinyl etherpolymers obtained by the process of the present invention by reactingsuch polymeric amines with polyisocyanates, such as p-toluenediisocyanate or polychlorocarbonates, for example, thebis-chlorocarbonate of diethylene glycol. The initial high molecularweight of the polymeric amine obtainable by the process of the presentinvention makes it possible to produce an ioneXchange resin with less ofthe polyfunctional cross-linkers, such as the diisocyanate, so thatthere is less decrease Such poly(sulfonvinylbenzene, divinyl' ether ofethylene glycol, diethylene 2' glycol dimethacrylate,divinylnaphthalene, diallyl phthaiate, divinyltoluene, trivinylbenzeneand any of the compounds listed in column 3, lines 10 to 44 of U. Patent2,647,886 which includes various allyl esters as well. as ethyleneglycol diacrylate, ethylene glycol dimethacrylate, ethyleneglycoldiethacrylate, glyceryl acrylate, and glyceryl dimethacrylate; andthen to hydrolyze at least 60% of the available amide groups to amines.This procedure produces high molecular weight copolymers containing apredominant proportion (from over 50 mole percent up to 95 mole percent)of an aminoalkyl vinyl ether cross-linked to a condition of insolubilityin organic and aqueous solvent media.

The following examples, in which the parts are by weight unlessotherwise noted, are illustrative of the present invention. In thefollowing examples, the copolymers designated polymer B, D, F, and Hrespectively were solublepolymers higher in molecular weight than thecorresponding homopolymers designated polymer A, C, E, and Grespectively. Polymer l is also an example of a soluble homopolymerwhich is readily hydrolyzable in accordance with the invention. PolymerJ is an example of an insoluble cross-linked polymer which can behydrolyzed to an insoluble ion-exchange resin.

EXAMPLE 1 (a) Polymerization of formamidoethyl vinyl etherpolymer A.-Asolution of 100 grams of formamidoethyl vinyl ether and 0.5 gram ofdimethyl azoisobutyrate was placed in a clean, dry vessel previouslyflushed with nitrogen. The solution was heated to 75 C. whereuponpolymerization began, the temperature rising to 100 C. as the result ofthe exotherm. After eight hours an additional 0.5 gram of initiatordissolved in 25 ml. of

dimethylformamide was added with stirring to the mixture and thereaction was continued at 75 C. to make a total of 23 hours. The polymerwas isolated by precipitation from solution with acetone and was driedat 60 C./0.2 mm. Hg to constant weight. A yield of 59 grams of viscous,water-soluble product was isolated. The molecular weight as determinedin an osometer was approximately 7500. A 50% aqueous solution had a Cardner-Holdt viscosity of 13+ (0.75 poise).

(b) Anaqueous solution of polymer A containing 12.5% of polymer washeated to 85 C. and treated dropwise (while stirring) with a 50%solution of sodium hydroxide containing two moles of alkali per mole ofamide. The addition was regulated so that complete solution wasmaintained. If polymer precipitated, addition was stopped until thatpolymer had redissolved. The mixture was heated for 12 hours at 85 C.after the addition and was ion-exchanged through a column containingboth anionand cation-exchange resins. The efiluent solution waspartially concentrated and analyzed for amine content by titration anddetermination of solids. The product was 86% hydrolyzed to the aminebeing essentially poly(aminoethyl vinyl ether).

(0) A solution of polymer A, 23 grams, in a mixture of water andisopropanol (150 grams/40 grams) was heatedand treated slowly with 80grams of 25% sodium hydroxide. The solution was heated and stirred atreflux for 16 hours. The solution was adjusted to pH 5.0 with dilutesulfuric acid and then treated with 45 grams of lead oxide and stirredfor one hour. The resultant alkaline slurry was filtered andconcentrated at reduced pressure to dryness. The residue was leachedwith methanol and the methanol solution filtered and dried to givetheproduct, poly(aminoethyl vinyl ether), 12.5 grams, containingapproximately 0.8 mole of primary amine per mole of vinyl unit.

(d) -A 20% aqueous solution of polymer A, freed of monomer byextractionwith benzene, was hydrolyzed by heating-with 25% aqueoussulfuric acid at 100 C. for one hour. The. solution was renderedalkalinewith sodium hydroxide and treated with excess benzenesulfonylchloride. The resultant sulfonamide was extracted with ethylenedichloride and purified by solution in alkali and reprecipitation withhydrochloric acid. The product was a brittle, tan solid at roomtemperature and melted at about 50 C. It contained 6.0% nitrogen and12.6% sulfur, being thus largely poly(benzenesulfonamidoethyl vinylether). Over of the available amide groups were hydrolyzed to aminegroups. The incorporation of 5% to 20% of the-poly(sulfonamide) productin copolymers of 80% to vinyl chloride with 5% to 20% of vinyl acetateproduces well-plasticized articles.

(e) The procedure of part (d) hereof was repeated substituting for thebenzenesulfonyl chloride in successive operations, (1)2,4-dichlorobenzenesulfonyl chloride and (2) p-nitrobenzenesulfonylchloride. The products obtained served as stomach poisons for chewinginsects, such as the armyworm.

(f) The procedure of part (d) hereof was repeated substituting for thebenzenesulfonyl chloride in successive operations (1) methylsulfonylchloride and (2) cyclohexylsulfonyl chloride. The products were goodplasticizers for copolymers of vinyl chloride and vinyl acetate whenappliedas in part (d) hereof.

EXAMPLE 2 (a) Copolymerization of formamidoetlzyl vinyl ether andN,N-bis-vinyloxyethylureap0lymer B.A mixture of grams of formamidoethylvinyl ether, 6.0 grams of N.N-bis-(vinyloxyethyl)urea, 40 grams ofdimethylformamide and 1.2 grams of dimethyl azoisobutyrate was slowlystirred in a nitrogen atmosphere and heated at 75 C. for 5 /2 hours.Thesoluble polymer was precipitated with acetone and dried well to give96 grams (80% conversion) of glossy product corresponding to a copolymerconsisting largely of units of formamidoethyl vinyl ether. A 25% aqueoussolution had a Gardner-Holdt viscosity of I (2.25 poise) and an osmoticmolecular weight of approximately 14,000.

(b) The polymer of part (a) hereof is hydrolyzed by the procedure ofExample l(b) except the time was 16 hours instead of 12 andthesodiurnhydroxide was added as a 25 solution although ratio of 2 moles of sodiumhydroxide to one of the amide was adhered to. The extent of hydrolysisto amino units was 86%.

(c) The product of Example 2(b) was dried and dissolved in benzene andtreated with a benzene solution of diisocyanatophenyl methane containing0.1 of the molar equivalent of the polyamine. The product thatprecipitated was washed and dried. It was a weak-base ionexchange resinwith a capacity of 4.0 meq./ g.

EXAMPLE 3 polymerized to poly-(acetamidoethyl vinyl ether) (obtained in92% conversion) with 2% by weight of dimethyl azoisobutyrate at 75 C.for 16 hours. A 25% aqueous solution had a Gardner-Holdt viscosity ofA-1.

(b) The polymer of part (a) hereof is hydrolyzed by the procedure ofExample l(b) except the time was 16 hours insteadof 12.= The extent ofhydrolysis to amino units was 84%.

(c) The polyamine of Example 3(b) obtained in the anhydrous state byfreeze-drying was dissolved in dry benzene and treated with anequivalent quantity of pnitrophenyl isocyanate in benzene. The product,poly(pnitrophenylureidoethyl vinylether), precipitated and was isolatedby filtration.

The product is useful as an insecticide, particularly as a stomachpoison in the control of chewing insects such as the armyworm.

EXAMPLE 4 (a) Polymer D.--A copolymer of 97 mole percent ofacetamidoethyl vinyl ether and N,N'bis-vinyloxyethylurea containing 3mole percent of the latter was prepared in 84% conversion by theprocedure of Example 2(a) used for making polymer B.

(b) The polymer of part (a) hereof is hydrolyzed by the procedure ofExample 1(b) except the time was 16 hours instead of 12 and the sodiumhydroxide was added as a 25% solution although ratio of 2 moles ofsodium hydroxide to one of the amide was adhered to. The extent ofhyrolysis to amino units was 84%.

(c) The polyamine of Example 4(b) in a mixture of benzene asd watercontaining an equivalent molar quantity of potassium carbonate wastreated with a molar equivalent of allyl chlorocarbonate at to 5 C. Theresultant product, poly(allyl N-vinyloxyethylcarbamate, was isolatedfrom the benzene layer by drying and concentration. The product was aviscous material which could be readily formulated into compositionsuseful for film-formation. The resultant films could be thermoset bybaking in the presence of air. This process was facilitated and mademore efficient by the incorporation of metallic driers such as cobalt ormanganese naphthenate. The resultant films were tough and completelyresistant to water, soap and common solvents.

(d) In place of the chlorocarbonate of Example 4(a) there wassubstituted an equivalent quantity of dimethylcarbamyl chloride and thereaction was conducted at to C. The product was a viscous, resinous massthat was useful as a plasticizer for cellulose esters such as acetate orbutyrate or combinations thereof. It was also useful as a plasticizerfor copolymers of acrylonitrile such as one comprising 70 parts ofacrylonitrile and 30 parts of ethyl acrylate. The product wascharacterized by permanence, lack of migration and good low-temperatureproperties.

EXAMPLE 5 (a) Polymer E.A polymer of N-methylformamidq ethyl vinyl etherprepared by the procedure of Example 1(a) used for making polymer A wasobtained in 90% conversion.

(b) The polymer of part (a) hereof is hydrolyzed by the procedure ofExample 1(b) except the time was 72 hours instead of 12 and the sodiumhydroxide was added as a 25 solution although ratio of 2 moles of sodiumhydroxide to one of the amide was adhered to. The extent of hydrolysisto amino units was 64%.

(c) The polyamine of Example 5 (b) in aqueous solution was treated withan equivalent quantity of benzyl chloride and sodium hydroxide, thechloride and hydroxide being added alternately in small portions. Themixture was maintained at 80 C. during the additions and for 4 hoursthereafter. The product, which was isolated by extraction with benzenewas essentially the polymeric tertiary amine,poly(N-benzyl-N-methylaminoethyl vinyl ether).

This material is an active fungicide giving complete control of bothMonilinia fructicola and Stemphylium sarcinaeforme at concentrations of0.1% or less.

EXAMPLE 6 (a) Polymer F.A copolymer of 98 mole percent ofN-methylformamidoethyl vinyl ether and 2 mole percent ofN,N'-bis-(vinyloxyethyl)urea made by the procedure used for makingpolymer B was obtained in 95% conversion.

A 24 hours.

(b) The polymer of part (a) hereofishydrolyzed the procedure of Example1(b) except the time was, 72,

hours insteadof 12 and the sodium hydroxide was added as a 25 solutionalthough ratio of 2 moles of sodium hydroxide to one of the amide wasadhered to.' The extent of hydrolysis to amino units was 66%.

EXAMPLE 7 (a) Polymer G.A 50% aqueous solution of 2- ureidoethyl vinylether was mixed with 1% by weight of dimethyl azoisobutyrate and allowedto polymerize at C. for 16 hours. The polymer was isolated as a solid byprecipitation with acetone and drying. A 50% aqueous solution ofpurified polymer had a Gardner-Holdt viscosity of U (6.3 poises) and anosmotic molecular weight of 50,000.

(b) A solution of 40 grams (0.3 mole) of polymer G in 200 ml. of waterwas heated to reflux and treated slowly with a solution of 25 grams ofsodium hydroxide in 270 ml. of water. The reaction was continued for Theammonia, evolved during the reaction, was collected and titrated andfound to be of theory. The mixture was purified by treatment with asulfonic acid ion-exchange resin in the acid form and concentrated atreduced pressure. The concentrated residue was frozen and dried in vacuoto give 33 grams of fine powder-readily soluble in water. It contained11.8% nitrogen equivalent to 73.5% of the theoretical primary aminegroups. lts approximate average molecular weight was 20,000.

This material is an extremely effective bactericide and in additiongives control of Coli T6, Streptococcus 7 and Staphylococcus P1 phagestrains.

(0) Handsheets were prepared from bleached and un-' bleached pulps eachcontaining 2% of the indicated resin The pulps were each at pH 6.9. Thesheets were then examined for wet-tensile strength by the usualprocedure.

Wet Tensile (7 days).

lbs/in. width Resin Unbleached Bleached Kraft Kraft 1. Product of part(a) hereof 8.0 4. 2 2. Poly (aminoethyl vinyl ether) 3. 2 1. 5 3. None 55 1 Polymer prepared by direct polymerization of aminoethyl vinyletheigvith an azo catalyst and consequently of low average molecularweig EXAMPLE 8 (a) Polymer H.-A copolymer containing 99 mole percent ofZ-ureidoethyl vinyl ether and 1 mole percent ofN,N-bis-vinyloxyethylurea was prepared by the same procedure as thatused for making polymer G. The copolymer had an osmotic molecular weightof 80,000.

(b) The polymer of part (a) hereof was hydrolyzed by the procedure ofExample 7(b). The extent of hydrolysis was about 71%.

EXAMPLE 9 EXAMPLE 10 Films of cellulose acetate were prepared containing10% by weight of the polymer of Example 2(b) in one case (film I) andthe polymer of Example 5(b) in the second (film II). Each was dyed witha direct, acid,

Gas-Fade Cycles Percent Soluble in Acetone Dye Pickup EXAMPLE 11 (a)Polymer J.A mixture of grams of formarnidoethyl vinyl ether, 2 grams ofdivinylbenzene, 1.0 gram of dirnethyl azoisobutyrate, and 20 ml. oftoluene was heated at 65 C. for 20 hours. A yield of 9.5 grams ofinsoluble material corresponding to a copolymer of the two monomers wasobtained.

(b) Half of the product of part (:1) hereof was hydrolyzed by, refluxingwith aqueous sulfuric acid and another half was hydrolyzed by refluxingwith sodium hydroxide.- The resultant products in which over 60% of theavailable amide groups were hydrolyzed to amine groups were useful asion-exchange resins, each having about 2.0 meq. of weal: base capacity/g.

Other preparations similarly obtained varied in activity from 1.5 g. to3 meq./g. depending on the amount of divinylbenzene and the degree ofhydrolysis obtained.

(0) The procedure of parts (a) and (b) is repeated, replacing thedivinylbenzene with 2 grams of divinyltoluene. Again, over 60% of theavailable amine groups are hydrolyzed and the product is useful as anionexchange resin.

(03) The procedure of parts (a) and (b) is repeated, replacing thedivinylbenzene with 2 grams of the divinyl ether of ethylene glycol.Again, over 60% of the available amine groups are hydrolyzed and theproduct is useful as anion-exchange resin.

I claim:

1. A process for producing a polymer of an aminoalkyl vinyl ether whichcomprises hydrolyzing in an aqueous alkaline medium at a temperature of80 C. to 100 C. a polymer, having an average molecular weight of at:least 5000, of a ureidoalkyl vinyl ether having the formula CH=CHOANRCONH wherein A is an alkylene group of 2 to 3 carbon atoms ofwhich at least two separate the adjoining O and N atoms, and R isselected from the group consisting of H and CH 2. A'process' forproducing an insoluble polymerof an aminoalkyl' vinyl ether whichcomprises hydrolyz'ing inan aqueous medium at a temperature of'80" C.to100 C. a copolymercomprising to mole percent of polymerized units of aureidoalkyl vinyl ether having the formula CH =CHOANRCONH wherein A isan alkylene group of 2 to 3 carbon atoms of which at least two separatethe adjoining O and N atoms, and R is selected fromthe group consistingof H and CH said copolymer being cross-linked to a conditionofinsolubility in both aqueous and organic solvent media with 5 to 20mole percent of polymerized units of a copolymerizable,polyethylenically unsaturated monomer selected from the group consistingof divinylbenzene, trivinylbenzene, divinyltoluene, divinyl ether ofethylene glycol, N,N'-bis-vinyloxyethylurea, ethylene glycol diacr ate,ethylene glycol dimethacrylate, ethylene-glycol diethacrylate, glyceryldiacrylate, glyceryl dimethacrylate, and diethylene glycoldimethacrylate, to form a crosslinked polymer of at least 50 molepercent of polymerized units of an'aminoalkyl vinyl ether WhlCh'iSinsoluble in aqueous and organic solvent media.

3. A process as defined in claim 2 in which the hydrolysis is effectedin anaqueous alkaline solution.

4. A process which comprises heating a copolymer of 80 to 95 molepercent of polymerized units of 2-ureidoethyl vinyl ether cross-linkedto a condition of insolubility in both aqueous and organic solvent mediaby 5 to 20 mole percent'of polymerized. units of a copolymerizable,polyethylenically unsaturated monomer selected from the group consistingof divinylbenzene, trivinylbenzene, divinyltoluene, divinyl ether ofethylene glycol, N,N'-bis-vinyloxyethylurea, ethylene glycol diacrylate,ethylene glycol dimethacrylate, ethylene glycol diethacrylate; glyceryldiacrylate, glyceryl dimethacrylate, and diethylene glycol'dimethacrylate, in an aqueous alkaline medium at an elevatedtemperature of 80 to l0\. C. and recovering'a cross-linked copolymer ofat least 50 mole percent of polymerized units of [3-vinyloxyethylaminewhich is insoluble in aqueous and organic solvent media.

References Cited in the file of this patent UNITED STATES PATENTS2,597,493 Hwa May 20, 1952 2,601,251 Bruson June 24, 1952 2,631,999McMaster et al Mar. 17, 1953 2,683,125 DAlelio July 6, 1954 2,686,173Sauer Aug. 10, 1954 2,734,890 Bortnick et a1 Feb. 14, 1956

1. A PROCESS FOR PRODUCING A POLYMER OF AN AMINOALKYL WINYL ETHER WHICHCOMPRISES HYDROLYZING IN AN AQUEOUS ALKALINE MEDIUM AT A TEMPERATURE OF80*C. TO 100*C. A POLYMER, HAVING AN AVERAGE MOLECUJAR WEIGHT OF ATLEAST 5000, OF A UREIDOALKYL VINYL ETHER HAVING THE FORMULA